(2-{[1-(Pyridin-2-yl)ethyl­idene]amino­meth­yl}pyridine-κ3N,N′,N′′)bis­(thio­cyanato-κN)zinc

Wang, C.-Y.; Li, J.-F.; Wu, X.; Tu, H.-Y.; Zhu, P.-F.

doi:10.1107/S1600536811043984

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page m1616

doi:10.1107/S1600536811043984

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(2-{[1-(Pyridin-2-yl)ethylidene]aminomethyl}pyridine-κ³N,N′,N′′)bis(thiocyanato-κN)zinc

Chen-Yi Wang,^a ^* Jing-Fen Li,^a Xiang Wu,^a Hai-Yu Tu ^a and Pei-Fei Zhu ^a

^aDepartment of Chemistry, Huzhou University, Huzhou 313000, People's Republic of China
^*Correspondence e-mail: chenyi_wang@163.com

(Received 25 August 2011; accepted 23 October 2011; online 29 October 2011)

The complete molecule of the title mononuclear zinc(II) complex, [Zn(NCS)₂(C₁₃H₁₃N₃)], is generated by crystallographic twofold symmetry, with the metal atom lying on the rotation axis. The pendant methyl group of the ligand is statistically disordered over two sites. The Zn²⁺ cation is coordinated by the N,N′,N′′-tridentate Schiff base ligand, and by two thiocyanate N atoms, forming a distorted ZnN₅ trigonal–bipyramidal geometry.

Related literature

For Schiff-base complexes reported by us, see: Wang & Ye (2011 ); Wang (2009 ); Wang et al. (2011 ). For similar zinc(II) complexes, see: Wang (2010 ); Huang (2011 ); Ikmal Hisham et al. (2011 ); Wang (2011 ).

Experimental

Crystal data

[Zn(NCS)₂(C₁₃H₁₃N₃)]
M_r = 392.79
Monoclinic, C 2/c
a = 14.272 (3) Å
b = 8.633 (3) Å
c = 15.338 (3) Å
β = 110.945 (2)°
V = 1764.9 (8) Å³
Z = 4
Mo Kα radiation
μ = 1.63 mm⁻¹
T = 298 K
0.17 × 0.13 × 0.12 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.769, T_max = 0.828
3113 measured reflections
1838 independent reflections
1395 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.109
S = 1.07
1838 reflections
111 parameters
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Zn1—N3	1.970 (3)
Zn1—N2	2.076 (4)
Zn1—N1	2.156 (3)

N1ⁱ—Zn1—N1	152.16 (16)
Symmetry code: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811043984/hb6391sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811043984/hb6391Isup2.hkl

checkCIF report

Comment top

Schiff bases and their complexes have been widely studied for their synthesis, structures, and biological activities. As part of our investigations into Schiff base complexes (Wang & Ye, 2011; Wang, 2009; Wang et al., 2011), we have synthesized the title compound, a new mononuclear zinc(II) complex, Fig. 1. The Zn atom in the complex is five-coordinated by the three N atoms of the Schiff base ligand, and by two thiocyanate N atoms, forming a distorted square pyramidal geometry. The Zn–N bond lengths (Table 1) are typical and are comparable with those observed in other similar zinc(II) complexes (Wang, 2010; Huang, 2011; Ikmal Hisham et al., 2011; Wang, 2011).

Related literature top

For Schiff-base complexes reported by us, see: Wang & Ye (2011); Wang (2009); Wang et al. (2011). For similar zinc(II) complexes, see: Wang (2010); Huang (2011); Ikmal Hisham et al. (2011); Wang (2011).

Experimental top

2-Acetylpyridine (1.0 mmol, 0.121 g) and 2-aminomethylpyridine (1.0 mmol, 0.108 g) were dissolved in MeOH (30 ml), to the mixture was added with stirring an aqueous solution (5 ml) of ammonium thiocyanate (2.0 mmol, 0.152 g) and zinc acetate dihydrate (1.0 mmol, 0.220 g). The final mixture was stirred at room temperature for 10 min to give a clear colorless solution. After keeping the solution in air for a week, colorless block-shaped crystals were formed at the bottom of the vessel.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level. Symmetry code: (i) 1–x, y, 1/2–z.

(2-{[1-(Pyridin-2-yl)ethylidene]aminomethyl}pyridine- κ³N,N',N'')bis(thiocyanato-κN)zinc top

Crystal data top

[Zn(NCS)₂(C₁₃H₁₃N₃)]	F(000) = 800
M_r = 392.79	D_x = 1.478 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.272 (3) Å	Cell parameters from 1062 reflections
b = 8.633 (3) Å	θ = 2.6–24.5°
c = 15.338 (3) Å	µ = 1.63 mm⁻¹
β = 110.945 (2)°	T = 298 K
V = 1764.9 (8) Å³	Block, colorless
Z = 4	0.17 × 0.13 × 0.12 mm

Data collection top

Bruker SMART CCD diffractometer	1838 independent reflections
Radiation source: fine-focus sealed tube	1395 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω scan	θ_max = 27.0°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→13
T_min = 0.769, T_max = 0.828	k = −10→7
3113 measured reflections	l = −19→18

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0552P)² + 0.5867P] where P = (F_o² + 2F_c²)/3
1838 reflections	(Δ/σ)_max < 0.001
111 parameters	Δρ_max = 0.59 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

[Zn(NCS)₂(C₁₃H₁₃N₃)]	V = 1764.9 (8) Å³
M_r = 392.79	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 14.272 (3) Å	µ = 1.63 mm⁻¹
b = 8.633 (3) Å	T = 298 K
c = 15.338 (3) Å	0.17 × 0.13 × 0.12 mm
β = 110.945 (2)°

Data collection top

Bruker SMART CCD diffractometer	1838 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1395 reflections with I > 2σ(I)
T_min = 0.769, T_max = 0.828	R_int = 0.023
3113 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.109	H-atom parameters constrained
S = 1.07	Δρ_max = 0.59 e Å⁻³
1838 reflections	Δρ_min = −0.40 e Å⁻³
111 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Zn1	0.5000	0.64025 (5)	0.2500	0.0552 (2)
S1	0.28816 (12)	0.97184 (15)	0.33736 (10)	0.1135 (5)
N1	0.42235 (19)	0.5802 (3)	0.10557 (18)	0.0607 (6)
N2	0.5000	0.3998 (4)	0.2500	0.0635 (10)
N3	0.3999 (2)	0.7781 (3)	0.2707 (2)	0.0700 (7)
C1	0.3860 (3)	0.6806 (4)	0.0353 (3)	0.0768 (10)
H1	0.3924	0.7862	0.0481	0.092*
C2	0.3395 (3)	0.6326 (5)	−0.0556 (3)	0.0885 (12)
H2	0.3137	0.7045	−0.1034	0.106*
C3	0.3318 (3)	0.4777 (6)	−0.0745 (3)	0.0943 (13)
H3	0.3019	0.4425	−0.1355	0.113*
C4	0.3682 (3)	0.3755 (5)	−0.0031 (3)	0.0822 (11)
H4	0.3624	0.2695	−0.0147	0.099*
C5	0.4139 (2)	0.4294 (4)	0.0865 (2)	0.0622 (8)
C6	0.4563 (3)	0.3228 (4)	0.1674 (3)	0.0693 (9)	0.50
C7	0.4455 (7)	0.1605 (7)	0.1517 (7)	0.093 (3)	0.50
H7A	0.5040	0.1085	0.1931	0.140*	0.50
H7B	0.4382	0.1386	0.0882	0.140*	0.50
H7C	0.3873	0.1248	0.1631	0.140*	0.50
C6'	0.4563 (3)	0.3228 (4)	0.1674 (3)	0.0693 (9)	0.50
H6'1	0.4030	0.2573	0.1720	0.083*	0.50
H6'2	0.5059	0.2564	0.1566	0.083*	0.50
C8	0.3551 (3)	0.8592 (4)	0.2993 (2)	0.0608 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0596 (3)	0.0491 (3)	0.0609 (3)	0.000	0.0265 (2)	0.000
S1	0.1452 (12)	0.1040 (9)	0.1163 (9)	0.0557 (8)	0.0772 (9)	0.0132 (7)
N1	0.0577 (16)	0.0650 (15)	0.0630 (16)	0.0002 (13)	0.0260 (12)	−0.0040 (12)
N2	0.064 (2)	0.054 (2)	0.074 (3)	0.000	0.0264 (19)	0.000
N3	0.0687 (18)	0.0654 (17)	0.0806 (19)	0.0099 (14)	0.0323 (15)	−0.0043 (15)
C1	0.083 (3)	0.076 (2)	0.073 (2)	0.0081 (19)	0.029 (2)	0.0052 (18)
C2	0.088 (3)	0.112 (3)	0.064 (2)	0.011 (2)	0.024 (2)	0.007 (2)
C3	0.092 (3)	0.123 (4)	0.064 (2)	0.008 (3)	0.023 (2)	−0.018 (2)
C4	0.084 (3)	0.084 (3)	0.076 (2)	−0.003 (2)	0.026 (2)	−0.021 (2)
C5	0.0584 (19)	0.0672 (19)	0.065 (2)	−0.0004 (16)	0.0263 (16)	−0.0130 (16)
C6	0.068 (2)	0.063 (2)	0.079 (2)	−0.0014 (16)	0.0287 (18)	−0.0115 (16)
C7	0.115 (7)	0.052 (4)	0.104 (6)	0.001 (4)	0.027 (5)	−0.003 (4)
C6'	0.068 (2)	0.063 (2)	0.079 (2)	−0.0014 (16)	0.0287 (18)	−0.0115 (16)
C8	0.064 (2)	0.0590 (18)	0.0593 (18)	0.0067 (16)	0.0224 (15)	0.0074 (15)

Geometric parameters (Å, º) top

Zn1—N3ⁱ	1.970 (3)	C1—H1	0.9300
Zn1—N3	1.970 (3)	C2—C3	1.364 (5)
Zn1—N2	2.076 (4)	C2—H2	0.9300
Zn1—N1ⁱ	2.156 (3)	C3—C4	1.356 (6)
Zn1—N1	2.156 (3)	C3—H3	0.9300
S1—C8	1.612 (3)	C4—C5	1.374 (5)
N1—C5	1.330 (4)	C4—H4	0.9300
N1—C1	1.336 (4)	C5—C6	1.489 (5)
N2—C6'ⁱ	1.368 (4)	C6—C7	1.421 (7)
N2—C6ⁱ	1.368 (4)	C7—H7A	0.9600
N2—C6	1.368 (4)	C7—H7B	0.9600
N3—C8	1.136 (4)	C7—H7C	0.9600
C1—C2	1.376 (5)

N3ⁱ—Zn1—N3	105.66 (17)	N1—C1—C2	122.0 (4)
N3ⁱ—Zn1—N2	127.17 (9)	N1—C1—H1	119.0
N3—Zn1—N2	127.17 (9)	C2—C1—H1	119.0
N3ⁱ—Zn1—N1ⁱ	100.08 (11)	C3—C2—C1	118.9 (4)
N3—Zn1—N1ⁱ	96.64 (11)	C3—C2—H2	120.5
N2—Zn1—N1ⁱ	76.08 (8)	C1—C2—H2	120.5
N3ⁱ—Zn1—N1	96.64 (11)	C4—C3—C2	119.2 (4)
N3—Zn1—N1	100.08 (11)	C4—C3—H3	120.4
N2—Zn1—N1	76.08 (8)	C2—C3—H3	120.4
N1ⁱ—Zn1—N1	152.16 (16)	C3—C4—C5	119.6 (4)
C5—N1—C1	118.6 (3)	C3—C4—H4	120.2
C5—N1—Zn1	115.8 (2)	C5—C4—H4	120.2
C1—N1—Zn1	125.6 (3)	N1—C5—C4	121.7 (3)
C6'ⁱ—N2—C6ⁱ	0.0 (3)	N1—C5—C6	116.3 (3)
C6'ⁱ—N2—C6	121.8 (4)	C4—C5—C6	122.0 (3)
C6ⁱ—N2—C6	121.8 (4)	N2—C6—C7	128.5 (5)
C6'ⁱ—N2—Zn1	119.1 (2)	N2—C6—C5	112.8 (3)
C6ⁱ—N2—Zn1	119.1 (2)	C7—C6—C5	118.7 (5)
C6—N2—Zn1	119.1 (2)	N3—C8—S1	178.2 (3)
C8—N3—Zn1	167.1 (3)

Symmetry code: (i) −x+1, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Zn(NCS)₂(C₁₃H₁₃N₃)]
M_r	392.79
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	14.272 (3), 8.633 (3), 15.338 (3)
β (°)	110.945 (2)
V (Å³)	1764.9 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.63
Crystal size (mm)	0.17 × 0.13 × 0.12

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.769, 0.828
No. of measured, independent and observed [I > 2σ(I)] reflections	3113, 1838, 1395
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.109, 1.07
No. of reflections	1838
No. of parameters	111
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.40

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Zn1—N3	1.970 (3)	Zn1—N1	2.156 (3)
Zn1—N2	2.076 (4)

N1ⁱ—Zn1—N1	152.16 (16)

Symmetry code: (i) −x+1, y, −z+1/2.

Acknowledgements

This work was supported financially by the Natural Science Foundation of China (No. 31071856), the Applied Research Project on Nonprofit Technology of Zhejiang Province (No. 2010 C32060), the Natural Science Foundation of Zhejiang Province (No. Y407318) and the Technological Innovation Project (sinfonietta talent plan) of college students in Zhejiang Province (Nos. 2010R42525 and 2011R425027).

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